JP2006316222A - Ink for marking pen excellent in resistance to pen tip drying - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink for marking pens which prevents a pen tip from being dried up for a long time and also can be formulated easily. <P>SOLUTION: The ink for marking pens excellent in pen tip drying resistance comprises at least a colorant, an organic solvent, a resin soluble in the organic solvent, a polyglycerol fatty acid ester expressed by general formula (1) and a disaccharide fatty acid ester (wherein, R represents a 12-26C acyl group or hydrogen, and n is an integer of 1-15). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  INDUSTRIAL APPLICABILITY The present invention is an ink for marking pens, and in particular, the pen tip is difficult to dry for a long time even when left with the cap removed, and is used as a general oil-based marking pen ink or as an erasable ink for writing boards. It is related with the ink for marking pens which was excellent in the dry resistance of the nib used.

  When a marking pen with a conventional volatile solvent as the main solvent is left in a state where the cap is removed (hereinafter referred to as “cap-off”), the pen tip dries and solidifies within a few hours (hereinafter referred to as “dry-up”). ") And writing was impossible. For example, those using sucrose esters (Japanese Patent Publication No. 1-49491 and Japanese Patent Publication No. 3-32590) and those using polyglycerin esters (Japanese Unexamined Patent Publication No. Hei 2-232277 and Japanese Patent Publication No. 3-49947). (Japanese Patent Publication No. 5-88749), or a combination of a polyglycerin ester and another substance (Japanese Patent Publication No. 7-72259) has been proposed, but they all have cap-off properties. There was no day and it was not practical.

  Under such circumstances, a combination of a disaccharide fatty acid ester and a sorbitan ester and / or a fatty acid triglyceride (JP 2001-335732 A) has been proposed. However, it was not effective without n-propanol and was not satisfactory due to formulation limitations.

Japanese Examined Patent Publication No. 1-49491 Japanese Patent Publication No. 3-32590 JP-A-2-232277 Japanese Patent Publication No. 3-49947 Japanese Patent Publication No. 5-88749 Japanese Patent Publication No. 7-72259 JP 2001-335732 A

  This invention is made | formed in view of this condition, and makes it a subject to provide the ink for marking pens which prevents the dry-up from a pen point over a long time, and there are few restrictions on a mixing | blending.

（Ｒは炭素数１２〜２６のアシル基又は水素を示し、ｎは１〜１５の整数を示す。） The invention according to claim 1 for solving the above-mentioned problems is at least a colorant, an organic solvent, a resin soluble in the organic solvent, a polyglycerin fatty acid ester represented by the following general formula (1), It is an ink for marking pens excellent in pen-tip drying resistance characterized by containing a disaccharide fatty acid ester.

(R represents an acyl group having 12 to 26 carbon atoms or hydrogen, and n represents an integer of 1 to 15)

  The polyglycerin fatty acid ester represented by the general formula (1) and the disaccharide fatty acid ester used in the present invention are simultaneously deposited when the solvent evaporates on the pen tip surface and the colorant or resin is deposited. Since a very brittle film is formed on the surface, evaporation of the solvent is prevented, and the film is broken by normal writing pressure, so that writing can be performed. In addition, since the disaccharide fatty acid ester promotes the film forming action of the polyglycerin fatty acid ester and more favorably forms a film that suppresses evaporation of the solvent, the disaccharide fatty acid ester is considered to further improve the dry-up preventing effect.

  In general, the colorant contained in the present invention includes oil-soluble dyes used in oil-based marking pen inks, Solbert dyes such as alcohol-soluble dyes, azo, anthraquinone, phthalocyanine or xanthan organic pigments and carbon black. Inorganic pigments such as titanium white can be used, and the content thereof is 0.5 to 35% by weight in the ink composition.

  As the organic solvent contained in the present invention, lower aliphatic alcohols and glycol ethers, particularly low-toxicity ethanol, n-propanol, isopropanol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are preferably used as the main solvent. The content thereof is 20 to 95% by weight in the ink composition.

  The resin contained in the present invention is used for securing the fixing of the ink and the dispersion stability of the pigment, rosin resin such as rosin, ester gum, rosin modified maleic resin, styrene maleic acid copolymer, Resins generally used in oil-based marking pen inks such as vinyl butyral, soluble phenol resin, formalin resin, and ketone resin can be used, and the content thereof is 1 to 30% by weight in the ink composition.

  The dry-up prevention effect in the present invention mainly depends on the evaporation rate of the solvent, and is the optimum value of the amount of n-propyl alcohol used in the invention of the above-mentioned JP-A No. 2001-335732. There is no. Of course, the higher the amount of n-propyl alcohol or glycol ether with a low evaporation rate, the higher the effect of preventing dry-up. However, even with the use of only ethyl alcohol with a high evaporation rate, the dry-up is more than 2 days. Maintain the prevention effect.

（Ｒは炭素数１２〜２６のアシル基又は水素を示し、ｎは１〜１５の整数を示す。） In the present invention, a polyglycerin fatty acid ester represented by the following general formula (1) is used as a dry-up preventing agent for improving the nib drying resistance.

(R represents an acyl group having 12 to 26 carbon atoms or hydrogen, and n represents an integer of 1 to 15)

  These are used as food additives and have high safety. Specifically, mono-fatty acid esterified with tri, tetra, penta, hexa, decaglycerin, and the like and fatty acids such as caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and bebenic acid. , Di, tri, penta, hepta, decaester and the like.

  Polyglycerin fatty acid esters having high dry-up prevention effects include hexaglyceryl tristearate (Japanese Patent Publication No. 2-232277), decaglyceryl pentastearate and hepta stearate (Japanese Patent Publication No. 7-72259). Can be mentioned.

  However, these polyglycerin esters have low solubility in alcohol solvents, and ink clay tends to be high. Therefore, when these are used, it is preferable to use polyglycerol lauric acid, oleic acid ester, stearic acid mono- and diester, etc., which have relatively good solubility. The content thereof is 0.05 to 12% by weight, preferably 0.2 to 6% by weight in the ink composition. However, only polyglycerin fatty acid esters can prevent dry-up only for about 5 to 18 hours at the maximum.

  Therefore, a disaccharide fatty acid ester is further used as a dry-up prevention aid. That is, a part of hydroxyl groups of altose type disaccharides such as maltose and lactose or trehalose type disaccharides such as trehalose and sucrose, such as propionic acid, caproic acid, caprylic acid, lauric acid, valmitic acid, stearic acid, bebenic acid, etc. It is esterified with a fatty acid, and examples thereof include disaccharide fatty acid monoesters, diesters, and triesters. Although some polyesters have a substitution number of 4 or more, it is not preferable because the ink becomes unstable over time due to low solubility in alcohol-based solvents. It is not something that lowers.

  In the present invention, even a disaccharide fatty acid ester having an HLB value of 5 to 10 is sufficiently effective, so that it can be used in a wider range than the case of JP-A-2001-335732. In addition, by using a polyglycerin fatty acid ester and a disaccharide fatty acid ester in combination, the effect of preventing dry-up can be increased several times to several tens of times as compared with the case of single use. In addition, although the said disaccharide fatty acid ester can be used even if individual or it mixes arbitrarily, the content shall be 0.05 to 10 weight% in an ink composition, Preferably it shall be 0.1 to 5 weight%.

  In addition, in order to obtain a writing board erasable ink of the type that can be erased by lightly rubbing with a dry cloth, etc., the handwriting written on the non-absorbing surface is dissolved in the organic solvent, and is hardly volatile. Alternatively, a non-volatile release agent may be added. Examples of the release agent include higher fatty acid esters, polyoxyethylene alkyl ethers, higher alcohols and the like.

Specifically, the higher aliphatic ester is preferably an ester of a higher fatty acid having 6 or more carbon atoms and a fatty acid alcohol having 3 or more carbon atoms, stearyl ethylhexanoate, isooctyl myristate, octyl palmitate, stearic acid. Examples thereof include isobutyl and isooctyl stearate. Examples of the polyoxyethylene alkyl ether include polyoxyethylene monoteuryl ether and polyoxyethylene monooleyl ether. Examples of higher alcohols include lauryl alcohol and oleyl alcohol.
These release agents may be used alone or in combination, and the content thereof is 1 to 25% by weight, preferably 3 to 15% by weight in the ink composition.

  The marking ink composition of the present invention can be easily obtained by mixing and dispersing the above-described components with a dispersing machine such as a homomixer, a ball mill, a roll mill, a sand mill, or a known stirrer.

  In the present invention, additives generally used in inks such as amines, dye solubilizers such as phosphate esters, penetrants such as benzyl alcohol and diacetone alcohol, and self-antioxidation agents can be further added.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.

Examples and comparative examples of erasable ink for writing boards (including either one of polyglycerin fatty acid ester and disaccharide fatty acid ester) are shown in Table 1, and examples of general oil-based marking pen inks and comparative examples (same as above) Is shown in Table 2. The numbers in the table represent weight% (wt%).
The erasable ink for writing board in Table 1 is obtained by mixing and dispersing a colorant (in this example, a commercially available product obtained by rolling a pigment and a resin) and ethanol with a homomixer for 3 hours, and then adding the remaining components. Further, a pen ink for marking was obtained by mixing and dispersing for 2 hours.
Moreover, the oil-based marking ink of Table 2 mixed and dispersed each component for 2 hours with the homomixer, and obtained the ink for marking pens.

（表１の補足説明）
（１）フジＡＳブルー：冨士色素（株）製[顔料：ピグメントブルー１５（５０ｗｔ％）
、樹脂：ポリビニルブチラール（５０ｗｔ％）]
（２）フジＡＳブラック：冨士色素（株）製[顔料：カーボンブラック（４５ｗｔ％）、
樹脂ポリビニルブチラール（５５ｗｔ％）]
（３）Ｈｅ．ＧＳ．２−Ｓ：ヘキサグリセリルジステアレート
（４）Ｈｅ．ＧＳ．３−Ｓ：ヘキサグリセリルトリステアレート
（５）Ｄｅ．ＧＳ．１−Ｌ：デカグリセリルモノラウレート
（６）Ｄｅ．ＧＳ．５−Ｓ：デカグリセリルペンタステアレート
（７）ショ糖エステル・Ｓ：ショ糖ステアリン酸エステル（ＨＬＢ １１：混合エステ
ル）
（８）ショ糖エステル・１−Ｓ：ショ糖モノステアリン酸エステル（ＨＬＢ １５）
（９）ショ糖エステル・１−Ｏ：ショ糖モノオレイン酸エステル（ＨＬＢ １５）
（１０）エマルゲン４０８：花王石鹸（株）製．ポリオキシエチレンオレイルエーテル Table 1

(Supplementary explanation of Table 1)
(1) Fuji AS Blue: manufactured by Fuji Color Co., Ltd. [Pigment: Pigment Blue 15 (50 wt%)
, Resin: polyvinyl butyral (50 wt%)]
(2) Fuji AS Black: Fuji Dye Co., Ltd. [Pigment: Carbon Black (45 wt%),
Resin polyvinyl butyral (55wt%)]
(3) He. GS. 2-S: hexaglyceryl distearate (4) He. GS. 3-S: hexaglyceryl tristearate (5) De. GS. 1-L: Decaglyceryl monolaurate (6) De. GS. 5-S: Decaglyceryl pentastearate (7) Sucrose ester S: Sucrose stearate (HLB 11: Mixed ester)
(8) Sucrose ester 1-S: Sucrose monostearate (HLB 15)
(9) Sucrose ester 1-O: Sucrose monooleate (HLB 15)
(10) Emulgen 408: manufactured by Kao Soap Co., Ltd. Polyoxyethylene oleyl ether

（表２の補足説明）
（１１）Ｒ−１３０８：バリファーストレッド ＃１３０８：オリエント化学工業（株）
製、油性染料
（１２）ＢＬ−６３６：バソニルブルー ＃６３６：ＢＡＳＦ社製、油性染料
（１３）ガムロジン：中華人民共和国製、ロジン変性グリセリンエステル
（１４）ケトン樹脂：ケトン樹脂Ｋ−９０：荒川化学工業（株）製
（１５）フェノール樹脂：タマノールー１００Ｓ：荒川化学工業（株）製、油溶性フェノ
ール樹脂
（１６）Ｐ．Ｇ．Ｍ．：プロピレングリコールモノメチルエーテル
（１７）Ｄｅ．ＧＳ．３−Ｓ：デカグリセリルトリステアレート
（１８）Ｄｅ．ＧＳ．７−Ｓ：デカグリセリルヘプタステアレート
（１９）ＴＡＭＮＯ−５：ＰＯＥ（５）オレイルアミン：日光ケミカルズ（株）製 Table 2

(Supplementary explanation of Table 2)
(11) R-1308: Bali First Red # 1308: Orient Chemical Industry Co., Ltd.
Manufactured, oil-based dye (12) BL-636: Basonyl blue # 636: manufactured by BASF, oil-based dye (13) gum rosin: manufactured by the People's Republic of China, rosin-modified glycerin ester (14) ketone resin: ketone resin K-90: Arakawa Chemical Industries (15) Phenol resin: Tamanol 100S: Arakawa Chemical Industries, oil-soluble phenol resin (16) P.I. G. M.M. : Propylene glycol monomethyl ether (17) De. GS. 3-S: Decaglyceryl tristearate (18) De. GS. 7-S: decaglyceryl hepta stearate (19) TAMNO-5: POE (5) oleylamine: manufactured by Nikko Chemicals Co., Ltd.

  Tables 3 and 4 show the test results of Examples 1 to 4 and Comparative Examples 1 to 5 of the erasable ink for writing board shown in Table 1. Table 5 shows the test results of Examples 5 to 8 and Comparative Examples 6 to 10 of the oil-based marking pen ink shown in Table 2.

試験方法
１）各インキを含浸させた中綿式マーキングペンのキャップを外してペン先を外部に露出
させ、気温２０℃、湿度５０％の室内に放置する。
２）開始から１２時間は３時間毎に、１２時間経過後は１２時間毎に筆記し、筆跡がかす
れる迄の時間を測定する。 Table 3

Test method 1) Remove the cap of the batting type marking pen impregnated with each ink, expose the pen tip to the outside, and leave it in a room with an air temperature of 20 ° C and a humidity of 50%.
2) Written every 3 hours for 12 hours from the start, and every 12 hours after the lapse of 12 hours, and measure the time until the handwriting is smeared.

試験方法
１）筆記性試験：気温２０℃、湿度５０％の条件下において、各インキを含浸させた中綿
式マーキングペンのキャップを外して、外部に露出させ、そのままの状態で４８時間
〔試験（１）〕及び７２時間〔試験（２）〕放置した後、市販のホワイトボードに筆
記して筆記線の状態を確認した。
２）インキを含浸させた中綿式マーキングペンにて市販のホワイトボード板に筆記後この
ボード板を気温２０℃、湿度５０％〔消去性試験（３）〕及び気温３０℃、湿度５０
％〔消去性試験（４）〕の条件下において、２４時間放置後、筆記線を布で軽く拭取
った。
３）インキを含浸させた中綿式マーキングペンにて市販のホワイトボード板に筆記後この
ボード板を気温２０℃、湿度５０％の条件下において、１４日間放置後、筆記線を布
で軽く拭い取った（消去性試験（５）〕。 Table 4

Test method 1) Writability test: Under the conditions of an air temperature of 20 ° C. and a humidity of 50%, the cap of the batting type marking pen impregnated with each ink is removed, exposed to the outside, and left as it is for 48 hours [Test ( 1)] and 72 hours [Test (2)] After standing, writing on a commercially available white board, the state of the writing line was confirmed.
2) After writing on a commercially available whiteboard board with a cotton-filled marking pen impregnated with ink, the board board was air temperature 20 ° C., humidity 50% [erasability test (3)], air temperature 30 ° C., humidity 50
% [Erasability test (4)] After leaving for 24 hours, the writing lines were gently wiped with a cloth.
3) After writing on a commercially available whiteboard board with a cotton-filled marking pen impregnated with ink, leave this board board for 14 days at 20 ° C and 50% humidity, and then gently wipe the writing line with a cloth. (Eraseability test (5)).

試験方法
１）気温２０℃、湿度５０％の条件下において、各インキを含浸させた中綿式マーキング
ペンのキャップを外して、ペン先を外部に露出させたまま放置する。
２）開始から２４時間は３時間毎に、
１日経過後は１日毎に筆記し、筆跡がかすれる迄の時間を測定する。 Table 5

Test Method 1) Under the conditions of an air temperature of 20 ° C. and a humidity of 50%, the batting type marking pen impregnated with each ink is removed, and the pen tip is left exposed to the outside.
2) 24 hours from the start every 3 hours,
After 1 day, write every day and measure the time until the handwriting fades.

  The marking pen ink of the present invention forms a coating on the surface of the pen tip that suppresses the permeation of the solvent more than the conventional invention, so that the pen tip can be used for a long time (as shown in Tables 3 and 5). Even if exposed to the outside for 5 days or more, particularly 5 days or more for oil-based marking pen inks, the solvent does not volatilize and writing becomes impossible. In addition, since the coating is thin and brittle, it is destroyed at the moment when pressure is applied to the pen tip, and the ink is smoothly discharged immediately after re-starting writing, so that it is extremely practical in that it does not cause blurring of the writing line. Yes (see Table 4). Furthermore, when used for marking pen ink for writing boards, it is excellent in high temperature (30 ° C.) erasability and erasability after standing for a long time (14 days). As described above, the marking pen ink of the present invention is extremely excellent in the nib-drying resistance when used in a writing instrument.

  Although the present invention has been described in some detail with respect to its most preferred embodiments, it will be apparent that a wide variety of different embodiments can be constructed without departing from the spirit and scope of the invention, the invention being defined by the appended claims. It is not restricted to the specific embodiment other than limiting in.

Claims (3)

Pen nib resistance comprising at least a colorant, an organic solvent, a resin soluble in the organic solvent, a polyglycerin fatty acid ester represented by the following general formula (1), and a disaccharide fatty acid ester Marking pen ink with excellent drying properties.

(R represents an acyl group having 12 to 26 carbon atoms or hydrogen, and n represents an integer of 1 to 15)   The organic solvent uses a lower aliphatic alcohol or glycol ether as its main solvent, particularly ethanol, n-propanol, isopropanol, propylene glycol monomethyl ether, or propylene glycol monomethyl ether acetate with low toxicity, The marking pen ink according to claim 1, wherein the content thereof is 20 to 95% by weight in the ink composition.   The resin is a rosin resin such as rosin, ester gum, rosin-modified maleic resin, styrene maleic acid copolymer, vinyl butyral, soluble phenol resin, formalin resin, or ketone resin. The ink for a marking pen according to claim 1 or 2, which is 1 to 30% by weight in the composition.